Polymeric compositions of acrylonitrile and chloro-allyl-tertiary amine



UnitedStates Patent POLYMERIC COMPOSITIONS OF ACRYLONITRILE AND CHLORO-ALLYL-TERTIARY AMINE Herman A. Bruson, Shaker Heights, Ohio, assignor to IndustrialtRayon Corporation, Cleveland, Ohio, a corporation of Delaware No Drawing. Application April 12, 1951, Serial No. 220,739

12 Claims. (Cl. 26041) This invention relates to new copolymers of acrylonitrile and to shaped articles formed therefrom such as, for

example, fibers, films and the like, hereinafter referred More particularly, this invention is con to as fibers. cerned with orientable fibers made from such polymeric materials and having improved dyeing properties.

It is already known in the art that allylamine and its homologues such as diallyl amine, triallyl amine, 2- methallyl amine, their salts or amides, e. g., N-diallylacetamide, are incapable of undergoing polymerization alone to form homopolymers or with other vinyl compounds to form copolymers, by any known methods (Parker, U. S. Patent No. 2,456,428).

It has now been found that copolymer compositions of acrylonitrile and chloro-allyl tertiary amines or salts thereof, may be prepared, which compositions are particularly adapted to the formation of oriented fibers possessing a very high afiinity for acid dyestuffs.

The new fiber-forming polymeric materials of the present invention comprise the polymerization product of a mixture comprising acrylonitrile and a chloro-allyl tertiary amine or a water-soluble salt thereof. The percentage of acrylonitrile in the polymer molecule is at least about 80% by weight and the percentage of the chloroamine or salt thereof is at least about 1% by weight. Advantageously, the percentage of chloroamine may be between about 1% and by weight, and preferably between about 2% and 10% by weight.

The chloro-allyl tertiary amines which are most useful for the purposes of the present invention have the formula wherein one X is chlorine and the other X is a mern;

ber of the group consisting of chlorine and hydrogen; a and b taken singly are members of the group consisting .of alkyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, carbalkoxyalkyl, ;'carboxyalkyl, aralkyl, aryl, or cycloalkyl radicals; and a and b taken jointly form a divalent radical,

said radical forming a fiveor six-membered heterocycle with the N atom.

and

" wherein X, N, a and b are as defined above.

Typical chloro-allyl tertiary amines useful for the purpose of this invention are, for example, the following:

N-dimethyl-Z-chloro-allylamine CH2=CCl-CH2N(CH3 2 N-diethyl-2-chloro-al1ylamine, N-(bis-n-hydroxyethyl) -2- chloro allylamine, N-(bis-fi-cyanoethyl) -2-chloro-allylamine, N-(bisB-carbomethoxyethyl) -2-chloro-allylamine "ice CH2=CC1CH2N(CH2CH2COOCH3)2, N (bis carboxymethyl) -2chloro-allylamine CH2 CCl-CH2N CHzCOOH) 2 N-(Z-chloro-allyl) methyl aniline CH2=CClCH2-N(CH3) CeH4 N-methyl-N-benzyl-Z-chloro-allylamine, N-methyl-N-cycloheXyl-Z-chloro-allylarnine, N-(2-chloro-allyl)-morpholine, N-(2-chloro-allyl) -piperidine, or the corresponding 3-chloro-allyl tertiary amines such'as N-dimethyl-3-chloroallylamine CHC1=CHCH2N(CH3)2, N-morpholin-3- chloro-allylamine CHCl=CHCH2NC4H3O, N-(bisp-cyanoethyl) -3-chloro-allylamine CHCl: CH- CHzN (CHzCHzCN) 2 and the corresponding 2,3-dichloro-allyl tertiary amines such as N-dimethyl-2,3-dichloro-allylamine CI-ICl: CC1 CHzN (CH3 2 and homologues thereof having the general formula designated herein above.

Instead of employing the chloroamine monomers in the form of their free bases, it is often more advantageous to use them in the form of their water-soluble salts. Such salts may be formed by the reaction of the chloroamines with inorganic or organic acids, or if desired, the salts can be in the form of water-soluble quaternary ammonium salts which can be made by the reaction of the chloroamines with various alkylating agents. In these situations, the anion portion of the salt is chemically united with the basic nitrogen atom of the chloroamine.

Typical of the monomeric chloro-allyl tertiary amine salts formed with acids are those obtained by treatment of the chloroamines with aqueous hydrochloric, sulfuric, nitric, phosphoric or boric acids, or organic acids such as formic, acetic, glycolic, lactic, crotonic, maleic, tartaric, phthalic, benzoic, citric, itaconic, acrylic, methacrylic, chloracetic, fumaric, oxalic, or other acids. Typical of the monomeric quaternary ammonium salts are those which can be prepared by reacting the free chloro-allyl tertiary amines with alkylating agents such as dimethyl sulfate, diethyl sulfate, methyl-p-toluene sulfonate, methyl bromide, ethyl iodide, benzyl chloride or other reactive organic halides or sulfates.

Shaped articles may be formed from suitable solutions of the above-mentioned copolymers by extruding the solutions into suitable coagulating media, e. g., evaporative atmospheres or liquid coagulating'baths. The shaped articles such as filamentary materials produced in this manner may then be treated to remove the residual solvent, and thereafter, stretched and heat treated so as to produce oriented products having high tenacity, high elastic recovery, low shrinkage, etc., and which possess a very high aflinity for acid dyestuffs.

This invention will be more fully described by the following examples, although, it is understood that the invention is not intended to be limited by these examples. In these examples percent of materials is intended to mean percent by weight.

Example I I The temperature was maintained by cooling at 60 C.

for 10 minutes after which an additional 1 gram of am monium persulfate and 0.5 gram of sodium bisulfite was added, and polymerization continued at 60-65 C. for 4 /2hours. The yield of white powdery copolymer (molecular weight about 30,000) after washing and drying was 179 grams, containing 3.1% by weight of copolymerized CHCl=CH-CH2NC4H O units therein.

The 1-chloro-3-N-morpholino-propene-1 used above is a colorless liquid B. P. 99-100 C. (17 mm.) obtainable by adding 110 grams of 1,3-dichloro-propene-1 to a stirred mixture of 40 grams of sodium hydroxide, 100 grams of water and 87 grams of morpholine at 50 C. After stirring for three hours at 6065 C., the mixture was cooled, extracted with ether and the ether extract was distilled in vacuo.

The dried copolymer obtained above was dissolved at about 95 C. in ethylene carbonate to form a solution containing 21% by weight of the copolymer. This solution after filtering and deaerating in vacuo, was heated to 120 C. and extruded through a spinneret having 40 holes (.003 inch diameter) into a coagulating bath consisting of 80% triethylene glycol and ethylene carbonate by weight. The bath temperature was maintained at about 120 C. while the coagulated filaments were drawn through the bath for inches of bath travel and then collected on a bobbin. The yarn was washed with water and then stretched ten-fold at 145 C. The stretched yarn was then reheated in relaxed condition at 150 C. whereupon it shrunk about 14%. The final yarn obtained was lustrous and strong; showing a tenacity of about 4.1 grams'per denier and an elongation of about 18% at break.

This yarn was dyed a deep orange by boiling for 30 minutes in an aqueous acid dye bath containing 0.2% to 2% sulfuric acid and 0.2% to 2% of the dyestuif known as Orange Y Conc. (Color Index 151). The dyed yarn thus obtained was then Washed and boiled with soapy water to remove any unabsorbed dye. After drying, the yarn was found to be evenly and intensely dyed and was fast to laundering. In contrast to the above, a sample of yarn spun in a similar manner from polyacrylonitrile could not be dyed under the same conditions.

(a) A skein of the above undyed yarn containing 3.1% by' weight of copolymerized CHCl=CHCI-Iz-NC4H3O units-in the copolymer was boiled for 30 minutes with a 0.2% solution of the acid dyestuff known as Brilliant Croceine 3BA acidified with 0.2% sulfuric acid. The yarn became dyed a deep maroon which did not wash out after repeated soapings.

(b) A similar skein of the undyed yarn was boiled for 30 minutes with a 10% solution of ethylene diamine in water. The yarn was then thoroughly washed with water and dyed at the boil for 30 minutes with a 0.2% solution of Brilliant Croceine 3BA acidified with 0.2% sulfuric acid. The resulting dyed yarn assumed a much deeper shade of maroon than that described in (a) above, and was fast to repeated soapings. In addition, the treatment with the ethylene diamine cross-linked the-polymer in'the fiber, rendering it insoluble in all organic solvents for polyacrylonitrile.

Example II N-dimethyl-Z-chloro-allylamine CH2=CC1CH2N(CH3) 2 was prepared by reacting aqueous 30% dimethylamine with 2,3-dichloropropene-1 in the presence of sodium hydroxide by the procedure described in Example I. It is a colorless liquid B. P. 110 C. (743 mm.).

To a stirred mixture of 1400 cc. of water and .20 grams of N-dimethyl-2-chloro-allylamine there was added 167 cc. of l-N sulfuric acid, followed by 180 grams of acrylonitrile. The mixture was maintained at 6668 C. while a solution of 3.5 grams of potassium persulfate in cc. of water was added, followed by 1.5 grams of sodium bisulfite. Polymerization continued for three hours at 6668 C. The white powdery copolymer was filtered off, washed with water, and dried. The yield was 160 grams and the product contained 0.8% chlorine corresponding to a content of 2.7% by weight of units in the copolymer. Fibers spun from this copolymer also have an improved affinity for acid dyestuffs.

Example III To a stirred solution of 1500 grams of water and 124 grams of 5% sulfuric acid at C. in an atmosphere of nitrogen, was added 3 grams of ammonium persulfate tained by cooling at 60 C. for 10 minutes after which an additional 1 gram of ammonium persulfate and 0.5 gram of sodium bisulfite was added, and polymerization continued at 60-65 C. for 4 /2 hours. The yield of white powdery coplymer (mol. wt. 30,000) after washing and drying was 164 grams, containing 1.06% chlorine. This corresponds to 4.8% by weight of copolymerized CH2=CClCHzNCiHaO units in the copolymer. Fibers spun therefrom have an afiinity for acid dyestuffs.

The 2-chloro-allyl morpholine used above is a colorless oil boiling at 89 C./18 mm. obtainable by reacting 2,3-dichloropropene-1 with morpholine in the presence of sodium hydroxide, according to the procedure described in Example I.

Example IV To a stirred mixture of 1350 cc. of water and 67.8 cc. of l-N sulfuric acid at 61 C. there was added 3.5 grams of potassium persulfate and 1.5 grams of sodium bisulfite, followed immediately by a mixture of 190 grams of acrylonitrile and 10 grams of N-diethyl-Z-chloro-allylamine.

The mixture was held for about 20 minutes at 6466 C. by suitable cooling, after which an additional 1 gram of potassium persulfate and 0.5 gram of sodium bisulfite was added. Stirring was continued at 60-66 C. for two hours longer after which the white powdery copolymer was filtered off, washed with hot water and dried at 65 C. for 24 hours. The yield was 181 grams and the average molecular weight was about 30,000. It contained 0.63% chlorine by analysis corresponding to a content of 2.6% by weight of N-diethyl-Z-chloro-allylamine in the copolymer. Fibers spun therefrom also have an improved afiinity for acid dyestuffs.

The N-diethyl-2-chloro-allylamine used above was prepared by gradually adding 112 grams of 2,3-dichloropropene-l to a stirred mixture of 40 grams of sodium hydroxide, grams of water, and 73 grams of diethylamine. After standing for 24 hours at room temperature, the mixture was boiled under reflux for three hours, then cooled, filtered, and the oil layer separated by means of ether. Upon distillation of the ether extract, 103 grams of the desired product boiling at 62 C./34 mm. was obtained as a colorless oil.

Example V N-diethyl-3-chloro-allylamine was prepared as in Example IV, except that 1,3-dichloropropene-1 was used in place of the 2,3-dichloropropene-1. It is a colorless oil boiling at 62 C./20 mm.

A mixture of grams of acrylonitrile and 10 grams of N-diethyl-3-chloro-allylamine was added to a stirred solution of 1350 cc. of distilled water, 67.8 cc. of l-N sulfuric acid, 4.2 grams of potassium persulfate and 1.8 grams of sodium bisulfite held at 60 C. in an atmosphere of nitrogen. Polymerization continued at 62-63 C. for about 15 minutes after which 1 gram of potassium persulfate and 0.5 gram of sodium bisulfite was added to complete the polymerization which required an additional 1% hours at 63 C.

The white powdery copolymer, after washing and drying, weighed 189 grams and contained 0.48% chlorine by analysis, corresponding to a content of 2% by weight of N-diethyl-3-chloro-allylamine in the copolymer. Its average molecular weight was about 40,000. It can be spun into fibers also having improved afi lnity for acid dyestuffs.

Example VI pyridine, ethyl acrylate, acrylamide, alpha-methacrylamide or other copolymerizable mono-olefinic compounds, in which cases "three component copolymers are obtained containing from about 5 to 7% by 'weight of 2-chloroallylpiperidine units.

tained 8.6%

Example VII l and 180 grams of acrylonitrile. The mixture was stirred at 6169 C. for about minutes after which an additional quantity of 2 grams of potassium persulfate and 2 grams of sodium bisulfite was added. Polymerization was continued at 697 1 C. for two hours. The powdery copolymer was filtered off, washed and dried. It conby weight of chloro-allyl-N-methylaniline units in its copolymer structure according to chlorine analysis. It can be spun into fibers having affinity for acid dyestuffs.

The 2-chloro-allyl-N-methylaniline used above is a pale yellow oil B. P. 132 C./ 18 mm. obtained by reacting 2,3- dichloropropene-l with N-methyl aniline in the presence of sodium hydroxide according to the procedure of Example I.

Example VIII To a stirred solution of 1400 cc. of distilled water and 10 cc. of glacial acetic acid in an atmosphere of nitrogen at 65 C., there was added a mixture of 182 grams of acrylonitrile and 18 grams of 1-chloro-allyl-N-diethanolamine CHzCHaOH CHG1=CH-CH2N CHzCHzOH followed immediately by a solution of 5.4 grams of potassium persulfate in 50 cc. of water, and 2.1 grams of sodium bisulfite added separately.

The temperature during polymerization was maintained by external cooling at 64-66 C. After seven hours stirring at 60 C., the white powdery copolymer was filtered off, washed thoroughly and dried at 65 C. for 24 hours. The product (yield 174 grams), contained 0.5% chlorine by analysis, corresponding to 2.5% by weight of units in the copolymer. This copolymer can be dissolved in an appropriate solvent such as, for example, ethylene carbonate, and spun to form strong, substantially white, fibers that have an afiinity for acid dyestufis.

The 1-chloro-allyl-N-diethanolamine used above is a colorless liquid boiling at 130 C./ .4 mm. obtained by reacting 1,3-dichloropropene-1 with diethanolamine and sodium hydroxide according to the procedure described in Example I.

As previously stated, the proportion of acrylonitrile in the oriented fiber should be at least about 80% by weight and preferably, at least about 90% by weight. A minor proportion (up to a total of about 10% by weight) of one or more other vinyl compounds can be copolymerized with the acrylonitrile and chloroamine monomers if desired, to yield tripolymers or tetrapolymers. Among such other monomers may be mentioned, for example: vinyl esters (vinyl acetate, vinyl formate, vinyl benzoate), vinyl ethers, and vinyl ketones; acrylic acid and its esters and amides; methacrylic acid and its esters, amides, and nitrile; maleic, itaconic, fumaric, crotonic acids and their esters, amides and nitriles; allyl alcohol and its esters and ethers; styrene and nuclear substituted styrenes, e. g. chloroand dichloro styrene; halogenated monoethylenic compounds such as vinyl chloride, vinyl fluoride, vinylidene chloride, 1,3-dichloro-propene-l, 1,2-dichloro-propene-2, allyl chloride, methallyl chloride, 2-chloro-allyl alcohol, and 1- allyloxy-3-chloro-2-propanol; N-vinyl compounds such as ing catalysts such as the above in combination with reducing agents such as sodium bisulfite, sodium hydrosulfite, etc., may be used with advantage.

The molecular weights of these copolymers are preterably within the range of 10,000 and 250,000 or even higher, although copolymers having molecular weights between 30,000 and 100,000 may be used with particular advantage in the production of fibers.

In the production of fibers from the acrylonitrilechloroamine copolymers, it is necessary to prepare solu tions thereof for extrusion into suitable coagulating media, i. e., evaporative or coatgulating atmospheres, liquid coagulating baths, etc. In general, these spinning solutions may be prepared by heating the finely divided copolymers in the presence of a suitable solvent at temperatures between about 50100 C. or higher depending upon the particular solvent being employed. Typical preferred solvents which may be used are various organic solvents such as N,N-dimethylformamide, or N,N-dimethylacetamide; or the non-nitrogen-containing solvents such as ethylene carbonate or the lactones, e. g. gamma-valerolactone, gamma-butyrolactone, etc. With advantage,-particularly in the production of fibers, the heated mixtures of polymer and solvent are maintained in inert or oxygen-free atmospheres to minimize discoloration. These spinning solutions may have a solids content between about 15% and 30% ,solids depending, among other factors, upon the temperature and upon the molecular weight of the polymer, and preferably between about 18% and 25%.

For various purposes it may be desirable to chemically and physically modify these polymer solutions by the presence of other materials such as, for example, pigments, plasticizers, stabilizers, spinning agents, etc.

Among the suitable liquid 'coagulants which may be employed with advantage with spinning solutions such as ethylene carbonate-type spinning solutions, may be mentioned glycol baths such as triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. ln general, the temperature of the ethylene carbonate-type spinning solution at extrusion may be maintained between about 80150 C., and the glycol coagulant at a temperature between about 50-150" C., or if desired, at a higsherC temperature such as, for example, up to about 17 The freshly extruded and coagulated material thereafter may be washed with an aqueous medium such as water andthe washed fibers subsequently stretched up to 600-1000 percent or more. Such stretching may be accomplished in secondary baths containing materials similar to those of the coagulating medium employed, or if desired, other heated media may be employed such as, for example, inert liquids, vapors or gases, e. g., steam.

The resulting oriented fibers can be dyed in acidified baths with the typical well-known acid dyestuffs such as, for example, Wool Orange, 36, Acid Brilliant Red 4BL, Fast Yellow YA, Acid Violet 4 BNS, Orange Y, Acid Scarlet 2B, Brilliant Croceine 3BA, and many others, by the usual techniques. In addition, these fibers can be treated with organic primary or secondary amines which react with the chlorine atom present in the polymer structure to form additional amino groups therein, and thereby give deeper shades when dyed with acid dyestuffs. Typical of such amines are the alkyl and di alkyl amines such as methyl or dimethylamine, ethanol amine, diethanolamine, morpholine, piperidine, and polyamines such as ethylene diamine, diethylene triamine, triethylene tetranline, etc. Treating the fibers with polyamines such as the above, causes the fibers to be crosslinked, rendering them insoluble in all organic solvents for polyacrylonitrile.

I claim:

1. As a new composition of matter, a copolymer derived by the polymerization of a mixture comprising acrylonitrile and an amino compound selected from the group consisting of a chloro-allyl tertiary amine, a water-soluble salt of said chloroamine formed with an acid, and a water-soluble quaternary ammonium salt of said chloroamine; said chloroamine having the formula whereinone X is chlorineand the other X is amember of the group. consisting of chlorine and hydrogen; "a and b taken singly :are members of the group consisting of alkyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, carbalkoxyalkyl, carboxyalkyl, aralkyl, .aryl, and cycloalkyl radicals; and a and b taken jointly form a divalent radical, said radical forming a heterocycle with the N atom, said heterocycle being selected from the group consisting of five-membered heterocycles and sixmernbered heterocycles; said. copolymer containing in thepolymer molecule atrleast about 80% by weight of acrylonitrile and at least about 1% by weight of said amino compound. I p

2.. As a new composition of matter, a copolymer derived by the polymerization of a mixture comprising acrylonitrile and N-dimethyl-Z-chloraallylarnine, said copolymer containing in the polymer molecule at least about 80% by weight of acrylonitrile and between about 2% and 10 by weight of said amino compound.

3. As a new composition of matter, a copolymer derived by the polymerization of a mixture comprising acrylonitrile and N-diethyl-2-chloroallylamine, said copolymer containing in the polymer molecule at least about 80% by Weight of acrylonitrile and between about 2% and 10% by weight of said amino compound.

4. As a new composition of matter, a copolymer derived by the polymerization of a mixture comprising acrylonitrile and N-mor pho1ino-2-chloroallylamine, said copolymer containing in the polymer molecule at least about 80% by weight of acrylonitrile and between about 2% and 10% by weight of said amino compound.

5. As a new composition of matter, a copolymer derived by the polymerization of a. mixture comprising acrylonitrilev and 1-chloro-allyl-N-diethanolamine, said copolymer containing in the polymer molecule at least about 80% by weight of acrylonitrile and between about 2% and 10% by weight of said amino compound.

6. As a new composition of matter, a copolymer de* rived by the polymerization of a mixture comprising acrylonitrile and N-piperidino-Z-chloroallylamine, said copolymer containing in the polymer molecule at least about 80% by weight of acrylonitrile and between about 2% and 10% by weight of said amino compound.

7. An oriented fiber having a molecular Weight between about 30,000 and 100,000 comprising the copolymer as defined in claim 1.'

8. An oriented fiber having a molecular weight between about 30,000 and 100,000 comprising the copolymer as defined in claim 2.

9. An oriented fiber having a molecular weight between about 30,000 and 100,000 comprising the copolymer as defined in claim 3. i

10. An oriented fiber having a molecular weight between about 30,000 and 100,000 comprising the copolymer as defined in claim 5.

11. An oriented fiber having a molecular weight between about 30,000 and 100,000 comprising the copolymer as defined in claim 4 which has been dyed with an acid dyestuif.

12. An oriented fiber having a molecular weight between about 30,000 and 100,000 comprising the copolymer as defined in claim 6 which has been dyed with an acid dyestufi.

References Cited in the file of this patent UNITED STATES PATENTS 2,491,471 Arnold Dec. 20, 1949 

1. AS A NEW COMPOSITION OF MATTER, A COPOLYMER DERIVED BY THE POLYMERIZATION OF A MIXTURE COMPRISING ACRYLONITRILE AND AN AMINO COMPOUND SELECTED FROM THE GROUP CONSISTING OF A CHLORO-ALLYL TERTIARY AMINE, A WATER-SOLUBLE SALT OF SAID CHLOROAMINE FORMED WITH AN ACID, AND A WATER-SOLUBLE QUATERNARY AMMONIUM SALT OF SAID CHLOROAMINE; AND CHLOROAMINE HAVING THE FORMULA 